Manufacture of calcium hypochlorite



' Ito Drawing.

' 'rite,ja relatively thin slurry can'be -.used

'30 hypochlorite, which Patented Apr. 15, 1930 UNITED STATES nonnn'r n. mcurrnnm AND mess mourns, or in semen, new roan, nssronons "PATENT OFFICE TO THE MA'I'I-IIEBON ALKAIQI WORKS, INC., NEW YORK, N. Y., A CORPORATION or vrnemrn, I

manner-nan or enncruu mocnnomn This invention relates to improvements in the production of calcium hypochlorite. f This invention provides an rofved method of producing. calcium hypoc orite which makes it possi f e to secnreaproduct of high purity and which hassjeyeral' .further important advantages in a mechanical as well as achemical aspect. I I i a In carrying out the present invention, calcium hypochlorite'formed by the chlorina tion of a slurry of lime is r-salted out,'for'example by the addition of sodium chloride. Bysubsetfilently adding. 'sodiumfc'hloride to promote t e separation of calcium hypoehlp 1n the chlorination operation, thu'smakingjit comparatively easy: to efiect substantially complete chlorination and also making it eas l ier to maintain agitation during-chlorination,-while at the same time a satisfactory recove' of calcium h hlorite' can be ob taine following the a ditionof salt,jthe calcium hypochlorite can be separated in a numher of ways, for example-b filtratiomaor by filtration followed-by mec anical pressing,

or by combined filtration and pressin'g The solution remaining after separationiofthe calcium hypochlorite may advantageously treated with lime to precipitate basic: calcium atter ma beusedinmak- Y ing up lime slurryto be su hed'to the chloria. nation 0 oration. The ad 'tionof salt, folc orination, tends to thicken or stifien the c orinated mixture and a part ofthe solution remaining after theseparatiolr'iof :cal- .cium hypochlorite may wit 'fiadvantage be .returned and added to the chlorinated mixture to which the salt is added "as a diluent without dissolving any ofthe'gprecipitimted calcium hy ochlorite. The separatefdrqcalacium hypoc orite is substantial y item calcium chloride, -:except as thatsaltis pres-E ent' in mother'liriuor remaininginthei recipitated materia Any-calcium chlori e so cipitated material with strong one of sodium hydroxide,v

chlorite.

by following example 10.5 lbsl of high L28 lbs. of water; an [slurry contains not more than about 1%,ot calcium hydroxide; About 9.4 lbs. of chlo- "r ne are required. '2.1' lbs. of finely event "by the amount be that worigin present canbe removed by the 'pre- SO llli or better sodium ihypo-a "chlorite compounds, but as the hme present a The invention will be becomes near application flled Auguat 4, 1996. Serial 1T0. 187,188.

grade lime (95% CaOH) are mixed with and sodium chloride are then added. Agitation 1s-- maintained during chlorination, and for about hr. afterthe addition of salt. The fieci-pitated calcium hypoclilorite can then separated in an convenient 'or desired manner. It may, or example, befiltered fromthesolution and then pressed. With a [pressure of from 500to 1,000 lbs. per-square inch, the content of motherliquor can be. reduced to about 20% of. the weight of the cake.

The 'separatedfiltrate is treated with 7.7 lbs.

chlorinated until the V of lime or less, which combines with calcium h'ypo'chlorite present to form a basic calcium hypochlorite which is precipitated. The precipitate is, with advantage, used in making up further quantities ofa lnne slurry to be sub- Leected to chlorination; the amount of lime to added for repetition of the operation being less than that originally. required in this precipitate; as" a basic h hlorite: The. amount of water to be add is also 1cm than ally required due to the water present m the precipitated basic hypochlo-' rite,- which may be returned to the chlorination operation while wet, and should be sufficient to maintain the ratio of calcium to ,water-at-the. end of the. chlorination opera tion the 'same'as in the first chlorination operation. In the subsequent chlorination of a slurry so pre ple about 7.0 l

rated from the basic calcium hypochlorite, which may be discarded. This solution may of limepresent in this 7 ared,less'chlorine, for exam- 1 is usually required. Most of the calcium chloride formed during chlorination is contained in the solution sepaalso contain some unrecoverable'calcium hypochlorite, -for example, an amount up to about 5% of the tot prwent in the system. The major part of the. chlorination may be carried out, with advantage, atfrom 30to 40 0., to minimize formation of bas c hypoyused up thetem perature may withadvantage be. reduced to about 20 to stirrer, for example, may be used during chlorination in carrying out this invention. When salt is added, however, the slurry be comes more diflicult to agitate unless a diluent such as a part of the mother liquor from which calcium hy hlorite has been separated is used. This particular diluent isof special value because it makes it possible to t in down the slurry without dissolving precipitated calcium hypochlorite or otherwise interfering with the operation. The diluent may be saturated with sodium chloride before it is added, and salt for salting out the hypo chlorite product may with advantage be supplied in the diluent. When a diluent is not employed, it may be desirable to employ some more powerful means for maintaining agitation, .for exam le a lunger type of agitator may be so use en salt 1s added to the chlorinated ixture, further uantities of calcium hy hlorite, that is C a(OCl) are precipitate The recovery is apparently highest when the amount of salt employed is somewhat short of that necessary to effect complete saturation of the liquor with sodium chloride.

As another examlple of the invention, 10.5 lbs. of 95% Ca(O 21 -are mixed with 37.4 lbs. of water' and t e mixture chlorinated with about 9.4 lbs of chlorine, and 6 lbs. of sodium chloride are then introduced. As a further example of the invention, 10.5 lbs. of (la-(OH); are mixed with 23.9 lbs. of water and chlorinated with about 9.4 lbs. of chlorine, and 1.5 lbs. of salt then introduced. It is particularly advantageous, in carrying out the present invention, to employ lime slurries within the range of concentrations of. the

two examples just given. The'use of a diluent in connection with the addition of salt is 'before drying, from any contaminating ca ar ticularly useful with slurries which be ore chlorination approach the concentration of the last example 'ust given.

The calcium y hlorite roduct, after separation from t e mother iquor, can be dried in any suitable manner, for example in an atmospheric drier or in a vacuum drier, to a water content of 1% or less. The product can be substantially freed, advantageousl cium chloride by treating it with su ient sodium hydroxide or sodium hypochlorite to convert any calcium chloride present to calcium hydroxide or calcium hypochlorite, respectively.

It will be apparent that the invention has several important advantages; The invention' makes it practicable to employ a relatively thin lime slurry. Complete chlorination is thus more easily effected, and unde-- sirable decomposition more easily avoided. The separation of the calcium hypochlorite product is also facilitated. At the same time, the slurry, particularly during the chlorination operation, is less diflicult to handle. By salting out of the calcium hypochlorite formed, a satisfactory recovery of the calcium hypochlorite can nevertheless be obtained. By using a thinner slurry instead of a thicker slurry, an equivalent yield or a yield increased as much as 10% or more may be obtained, in accordance with this invention, by the addition of salt which is an operation much less difficult than the further chlorination of thick slurries. It will also be apparent that the invention provides an improved method of recovering available chlorine from the mother liquor remaining after separation of the calcium hypochlorite product by precipitation with llme in the form of a basic hypochlorite available for use in the making of further quantities of slurry to be subjected to chlorination. Any excess of lime added to the motherliquor for precipitation of basic calcium hypochlorite is thus also returned to the chlorination operation with the precipitated basichypochlorite.

When sodium chloride is present in the beginning of the chlorination some of the calcium hypochlorite may be precipitated from solution during the chlorination, and, if sufiicient sodium chloride ispresent at the outset. or'is added during the chlorination, the calcium hypochlorite will be for the most part thrown out of solution during the chlorination. We regard it as more advantageous however to carry out the chlorination first and add the sodium chloride afterward, since by doing so a relatively thin slurry can be used in the chlorination operation and the calcium hy ochlorite salted out therefrom after the ch orination is completed.

We claim:

' 1. A process of making calcium hypochlo- I Operation being carried out with the simultaneous addition of a diluent solution substantially saturated with calcium hypochlorite.

. 4. A process of making calcium hypochlorite which comprises chlorinating a lime slurry and promoting the separation of calcium hypocholrite by the addition of sodium chloride, and employing the solution remaining after separation of the calcium hypochlorite as a diluent in connection with the addition of sodium chloride to promote the separation of calcium hypochlorite in the process.

5. A process of making calcium hypochlo- I rite which comprises chlorinating a lime slurry and separatlng calclum hypochlorlte from the chlorlnating mixture, adding lime to the solution remaining after separation of calcium hypochlorite and thereby precipitating basic calcium hypochlorite together with any excess lime, and supplying the precipitated material to a subsequent chlorination operation.

6. A process of making calcium hypochlorite which comprises precipitating a basic calcium hypochlorite from a calcium hypochlorite solution by the addition of lime, scparating the precipitate, and subjecting the separated precipitate to chlorination.

7. A process'of making calcium hypochlorite which comprises chlorinating a lime slurry containing not more than about 37 lbs. of water and not less than about 24 lbs.

of water per 10 .lbs. of lime and' salting out calcium hypochlorite from the chlorinated mixture.

8. A process of makin calcium hypochlorite which comprises c ilorinating a lime slurry containing not morethan about 37 lbs. of water'and not less than about 24 lbs.

of water per 10 lbs. of lime and promoting a the separation of calcium hypochlorite from the chlorinatedmixture by the addition of sodium chloride.

9. A process otm'akin calcium hypochlorite which comprises 0%10rinating a lime slurry, and promoting the separation of calciumhypochlorite by the addition of sodium chloride, at least a part of the sodium chlov ride being supplied dissolved in a diluent.

Iii-testimony whereof we aflix our signatures.

ROBERT B. MAGMULLIN. JESSE A. GUYER. 

